CN1659224A - Propylene copolymer compositions having a good low-temperature impact toughness and a high transparency - Google Patents

Propylene copolymer compositions having a good low-temperature impact toughness and a high transparency Download PDF

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CN1659224A
CN1659224A CN03813426.8A CN03813426A CN1659224A CN 1659224 A CN1659224 A CN 1659224A CN 03813426 A CN03813426 A CN 03813426A CN 1659224 A CN1659224 A CN 1659224A
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propylene copolymer
copolymer compositions
propylene
weight
propene polymer
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CN1290917C (en
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A·福赫斯
F·莫尔哈德
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Basell Polyolefine GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Abstract

The present invention relates to a propylene copolymer composition comprising A) a propylene polymer containing from 0 to 10% by weight of olefins other than propylene and B) at least one propylene copolymer containing from 5 to 40% by weight of olefins other than propylene, where the propylene polymer A and the propylene copolymer B are present as separate phases and the propylene copolymer composition has a haze value of <=30%, based on a path length of the propylene copolymer composition of 1 mm, and the brittle/tough transition temperature of the propylene copolymer composition is <=-15 DEG C.

Description

Have the good low-temperature impact toughness and the propylene copolymer compositions of high transparent
The present invention relates to propylene copolymer compositions, produce the method for propylene copolymer compositions, propylene copolymer compositions of the present invention is used for the purposes of producd fibers, film or moulded parts, and the fiber, film or the moulded parts that comprise propylene copolymer compositions of the present invention.
Propene polymer is a kind of plastics of the most frequent use now.Normally used propene polymer has isotactic structure.They can be processed into formed body, and it has favourable mechanical property, particularly high rigidity, stiffness and shape stability.The consumption goods of being made by propene polymer are used for various application, for example as plastic containers, family or office's goods, toy or labware.Yet product of the prior art does not have the desired comprehensive low-temperature impact toughness of many application and the good transparency and the good stress proterties that bleaches.
As everyone knows, the heterophasic propylene copolymers that has good impelling strength especially at low temperatures can utilize ziegler-natta catalyst systems to prepare in multistage polyreaction.Yet adding has the ethylene-propylene copolymer of ethene at high proportion in polymeric matrix, and this is necessary for improving low-temperature impact toughness, can make heterophasic propylene copolymers opaque.Flexibility causes being separated with the miscibility of the difference of polymeric matrix, and therefore causes the transparence value of the muddiness and the difference of non-homogeneous copolymer.In addition, utilize the ethylene-propylene rubber(EPR) of common Ziegler-Natta catalyst preparation also to have very uneven composition.
Also the heterophasic copolymer of known propylene can use the metallocene catalyst system preparation.Use the propene polymer of metallocene catalyst system preparation to have low extracted content, uniform comonomer distribution and good organoleptic properties.
The shortcoming of disclosed propylene heterophasic copolymer is that their fusing point is too low among the WO 94/28042, and this stiffness and thermal deformation resistant to multipolymer has disadvantageous effect.In addition, toughness neither be gratifying.
EP-A 433986 has described the heterophasic propylene copolymers with syndiotactic structure, and it uses specific metallocene catalyst system preparation.These propylene copolymer compositions have low relatively fusing point, and therefore have low stiffness and low thermal deformation resistant.
EP-A 1 002 814 has described the heterophasic copolymer of propylene, and it shows the balance of the excellence between stiffness, impelling strength and the thermal deformation resistant.
WO 01/48034 relates to metallocene compound, utilizes this compound to prepare the propylene copolymer with high molecular weight and high copolymerization of ethylene content under the relevant polymerizing condition of industry.Can prepare heterophasic propylene copolymers like this with high stiffness/impelling strength level.
Yet the shortcoming of disclosed heterophasic propylene copolymers is do not obtain gratifying low-temperature impact toughness and good transparency and simultaneously good stress whitening proterties comprehensive in the prior art.Described product perhaps has still not satisfied low-temperature impact toughness, perhaps still has unsafty transparency and stress whitening value.
An object of the present invention is to overcome the shortcoming of above-mentioned prior art and propylene copolymer compositions is provided, said composition has the comprehensive of good low-temperature impact toughness and good transparency and good stress whitening proterties, have higher melt, high stiffness and good thermal deformation resistant simultaneously, have low extracted content, comonomer distribution and good organoleptic properties uniformly simultaneously.
Have been found that this purpose reaches by propylene copolymer compositions, this propylene copolymer compositions comprises:
A) propene polymer, its comprise 0 to 10% weight the alkene that is different from propylene and
B) at least a propylene copolymer, it comprises the alkene that is different from propylene of 5 to 40% weight,
Wherein, propene polymer A exists as isolating mutually with propylene copolymer B, and
Based on the path length of 1 millimeter propylene copolymer compositions, the haze value of propylene copolymer compositions≤30%, and the fragility of propylene copolymer compositions/ductility transmition temperature≤-15 ℃.
In addition, had been found that the method that is used to prepare propylene copolymer compositions, propylene copolymer compositions is used for the purposes of producd fibers, film or moulded parts, and preferably as basal component, comprises fiber, film or the moulded parts of propylene copolymer compositions of the present invention.
The propene polymer A that is present in the propylene copolymer compositions of the present invention exists as isolating mutually with the propylene copolymer that exists as B component.Propylene copolymer compositions with this class formation also is called as heterophasic propylene copolymers, heterogeneous propylene copolymer or propylene-based block copolymer.
In heterophasic propylene copolymers composition of the present invention, propene polymer A forms three-dimensional bonding phase usually, and propylene copolymer B is embedded in wherein mutually.Disperseed the bonding phase of this class of one or more other phases usually to be called as matrix therein.Matrix also accounts for the main part by weight of polymer composition usually.
In heterophasic propylene copolymers composition of the present invention, propylene copolymer B usually is dispersed in the matrix with the form of fine dispersion.In addition, the isolating phase of propylene copolymer B typically has a diameter from 100 nanometers to 1000 nanometers.
Preferred geometry has the thickness of 100 nanometers to the length and 100 to 300 nanometers of 1000 nanometers.The mensuration of the geometry of the independent phase of propylene copolymer compositions can for example be undertaken by the evaluation of contrast transmission type microscope photograph (TEMs).
In order to prepare the propene polymer that is present in the propylene copolymer compositions of the present invention, except that propylene, at least a other alkene is used as monomer.As comonomer among the propylene copolymer B and the comonomer among the propene polymer A randomly, all are different from the alkene of propylene, and alpha-olefin especially promptly has the hydro carbons of terminal double link, all is possible.Preferred alpha-olefin is the straight or branched C that is different from propylene 2-C 20-1-alkene, especially straight chain C 2-C 10-1-alkene or side chain C 2-C 10-1-alkene, 4-methyl-1-pentene for example, conjugation and unconjugated diolefine be 1,3-butadiene, 1 for example, and 4-hexadiene or 1,7-octadiene or vinyl aromatic compounds be the vinylbenzene of vinylbenzene or replacement for example.The alkene that is fit to comprises that also wherein two keys are the alkene of the part of ring texture, and it can comprise one or more ring systems.Example is cyclopentenes, norbornylene, tetracyclododecen or methyl norbornylene or diolefine for example 5-ethidine-2-norbornylene, norbornadiene or ethyl norbornadiene.The mixture and the propylene of all right two or more alkene of copolymerization.Especially preferred alkene is ethene and straight chain C 4-C 10-1-alkene, for example 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene, especially ethene and/or 1-butylene.
The propene polymer A that is present in the propylene copolymer compositions of the present invention can be the propylene copolymer of alfon or the alkene that is different from propylene that comprises maximum 10% weight.Preferred propylene copolymer comprises 1.5 to 7% weight, the especially alkene that is different from propylene of 2.5 to 5% weight.As comonomer, preferably use ethene or straight chain C 4-C 10-1-alkene or its mixture, especially ethene and/or 1-butylene.Propene polymer A preferably has isotactic structure, and it is middle finger hereinafter, and except that a small amount of defective, all methyl side groups are arranged in the same side of polymer chain.
The B component that is present in the propylene copolymer compositions of the present invention is made up of at least a propylene copolymer that comprises the alkene that is different from propylene of 5 to 40% weight.Two or more different mutually propylene copolymers also are possible as the situation that B component exists; These propylene copolymers can be different on the amount of the copolymerization alkene that is different from propylene and type.Preferred comonomer is ethene or straight chain C 4-C 10-1-alkene or its mixture, especially ethene and/or 1-butylene.In other embodiment preferred, additionally used the monomer that comprises at least two two keys, for example 1,7-octadiene or 1,9-decadiene.The content that in propylene copolymer, is different from the alkene of propylene be typically 7 to 25% weight, preferred 10 to 20% weight, especially preferred 12 to 18% weight and especially 14% weight to 17% weight, based on propylene copolymer B.
The weight ratio of propene polymer A and propylene copolymer B can change.Be preferably 90: 10 to 60: 40, especially preferred 80: 20 to 60: 40 and very especially preferred 70: 30 to 60: 40.At this, propylene copolymer B comprises that all form the propylene copolymer of B component.
The haze value of propylene copolymer compositions of the present invention is≤30%, preferred≤25%, more preferably≤20%, especially preferred≤15% and preferred≤12% very especially, based on the path length of 1 millimeter propylene copolymer compositions.Haze value is the yardstick of measurement of species turbidity, therefore is the parameter that characterizes the propylene copolymer compositions transparency.Haze value is low more, and transparency is high more.In addition, haze value also depends on path length.Layer is thin more, and haze value is low more.Haze value is usually measured according to standard A STM D1003, can use different specimen, and for example thickness is that 1 millimeter injection-molded specimen or thickness is for example 50 microns film.According to the present invention, it is that the haze value of 1 millimeter injection-molded specimen characterizes that propylene copolymer compositions utilizes thickness.
In addition, the fragility of propylene copolymer compositions of the present invention/ductility transmition temperature be≤-15 ℃, preferred≤-18 ℃ and especially preferred≤-20 ℃.Very particularly preferably fragility/ductility transmition temperature be≤-22 ℃, especially≤-26 ℃.
Propene polymer at room temperature is a toughness material, promptly only before the material fracture viscous deformation takes place under mechanical stress.Yet under the temperature that reduces, propene polymer shows brittle rupture, does not promptly substantially have to be out of shape or to rupture under high spread rate.The parameter of the temperature that description distortion proterties changes from toughness to fragility is " fragility/ductility transmition temperature ".
In propylene copolymer compositions of the present invention, propene polymer A usually exists as matrix and the propylene copolymer B that has the stiffness that is lower than matrix usually and play the impact modifying agent effect is dispersed in the matrix with the fine dispersion form.This class impact modifying agent not only improves toughness at elevated temperatures, and reduces fragility/ductility transmition temperature.For purpose of the present invention, fragility/ductility transmition temperature utilization is measured according to the punching press of ISO 6603-2, and wherein temperature reduces with continuous stride.Distortion proterties when the power/displacement figure of record can be summed up specimen and is stretched under corresponding temperature in punching press test, thus fragility/ductility transmition temperature can be measured.In order to characterize sample of the present invention, temperature reduces with 2 ℃ stride, and fragility/ductility transmition temperature is defined as such temperature, and total deformation is lower than the preceding average total deformation of measuring for 5 times at least 25% under this temperature; This total deformation be when power through maximum value and be reduced to this maximum value power 3% the time drift motion displacement.Sample do not show sharp transition and wherein none measure to satisfy under the situation of criterion of regulation, the total deformation under 23 ℃ is used as reference value, and fragility/ductility transmition temperature is the temperature that total deformation is lower than the total deformation at least 25% under 23 ℃.
In addition, propylene copolymer compositions of the present invention shows good stress whitening proterties.For purpose of the present invention, stress whitening is the variable color of turning white that takes place in standing the zone of stress when polymkeric substance stands mechanical stress.Generally speaking, suppose that white variable color is caused by the little space that forms under mechanical stress in polymkeric substance.Good stress whitening proterties refers to not take place under mechanical stress or the variable color of only turning white in considerably less zone.
A kind of method that quantizes the stress whitening proterties be will definition the specimen shock stress that stands to define, measure the size of the white point that causes then.Therefore, according to DIN 53443 parts 1, in the vault method, dart is dropped on the specimen in the dart equipment.In the method, the dart with 250 gram masses and the drift of 5 mm dias have been used.It is 50 centimetres with the journey that falls that the vault radius is 25 millimeters.The specimen of using is injection-molded disk, and it is 2 millimeters with thickness that its diameter is 60 millimeters, and each specimen stands shock test only once.Stress whitening is reported with the diameter (unit millimeter) in visible stress whitening zone; Bao Gao value is the average of 5 specimen in each case, and single value measures as the average of two values, promptly the value in the flow direction of injection moulding and with the value that takes place on the bump opposite circular side with the vertical direction of flow direction.
Propylene copolymer compositions of the present invention is measured down at 23 ℃ according to the vault method, does not show or only show few stress whitening.Under preferred propylene copolymer compositions situation, 23 ℃ of mensuration, the value of mensuration is 0 to 8 millimeter, preferred 0 to 5 millimeter and 0 to 2.5 millimeter especially by the vault method.Very especially preferred propylene copolymer compositions is tested under 23 ℃ by the vault method, does not show stress whitening.
Propylene copolymer compositions of the present invention usually also comprises the well known by persons skilled in the art common additive of common amount, for example stablizer, lubricant and releasing agent, filler, nucleator, static inhibitor, softening agent, dyestuff, pigment or fire retardant.Generally speaking, these are introduced between the granulation stage of the powder-product for preparing in polymerization.
Common stablizer comprises for example sterically hindered phenol, processing stabilizers for example calcium stearate or Zinic stearas or dihydrotalcite, bulky amine or ultra-violet stabilizer of phosphorous acid ester or phosphinate, acid scavenger for example of oxidation inhibitor.Generally speaking, propylene copolymer compositions of the present invention comprises one or more stablizers, and its amount is maximum 2% weight.
Lubricant that is fit to and releasing agent are for example lipid acid, fatty acid calcium or fatty acid zinc salt, fatty acid amide or low-molecular-weight polyolefin wax, and it uses with the concentration of maximum 2% weight usually.
Possible filler is for example talcum, chalk or glass fibre, and these use with the amount of maximum 50% weight usually.
The example of the nucleator that is fit to is for example talcum, silicon-dioxide or kaolin, monocarboxylic acid or multi-carboxylate of inorganic additives, for example Sodium Benzoate or p t butylbenzoic acid aluminium, dibenzylidene sorbitol or its C 1-C 8-alkyl-substitutive derivative, for example methyl dibenzylidene sorbitol, ethyl dibenzylidene sorbitol or dimethyl dibenzylidene sorbitol, the perhaps salt of the diester of phosphoric acid, for example 2,2 '-methylene-bis (4,6-two-tert-butyl-phenyl) phosphoric acid ester sodium.The nucleator content of propylene copolymer compositions usually is maximum 5% weight.
This class additive is usually commercially available to be got, and is described in for example G  chter/M ü ller, Plastics Additives Handbook, the 4th edition, HansaPublishers, Munich, 1993.
In preferred embodiments, propylene copolymer compositions of the present invention comprises 0.1 to 1% weight, preferred 0.15 to 0.25% weight nucleator, particularly dibenzylidene sorbitol or dibenzylidene sorbitol derivative, especially preferred dimethyl dibenzylidene sorbitol.
The character of propylene copolymer compositions of the present invention is determined by the second-order transition temperature of propylene copolymer B basically.A kind of method that mensuration is present in the second-order transition temperature of the propylene copolymer B in the propylene copolymer compositions is to utilize DMTA (dynamic mechanics heat analysis) that propylene copolymer compositions is tested, and wherein measures the distortion of sample under the effect of sine swing power as the function of temperature.At this, measured spoke and phase shift the relation of shaking of distortion to compelling force.The second-order transition temperature of the propylene copolymer B of preferred propylene copolymer compositions is-20 ℃ to-40 ℃, preferred-25 ℃ to-38 ℃, especially preferred-28 ℃ to-35 ℃ and very especially preferred-31 ℃ to-34 ℃.
The second-order transition temperature of propylene copolymer B is formed decision by it basically, and particularly the ratio by the copolymerization comonomer that is different from propylene determines.Therefore the second-order transition temperature of propylene copolymer B can utilize the monomeric type of the polymeric that is used for propylene copolymer B and its ratio to control.For example, using propylene-ethylene copolymers to prepare as propylene copolymer B under the situation of propylene copolymer compositions, the ethylene content of 16% weight is corresponding to-33 ℃ to-35 ℃ second-order transition temperature.
The composition that is present in the propylene copolymer B in the propylene copolymer compositions of the present invention is preferably uniform.This makes their heterogeneous propylene copolymers common with using the Ziegler-Natta catalyst polymeric different, because use Ziegler-Natta catalyst to cause comonomer in addition under low comonomer concentration the mode with block introduce propylene copolymer, and irrelevant with polymerization process.For purpose of the present invention, term " mode with block is introduced " is meant that two or more comonomer units directly interconnect.
Under the propylene copolymer compositions situation of propylene and ethene acquisition, the structure of propylene-ethylene copolymers B can be utilized preferred 13The C-nuclear magnetic resonance spectroscopy.The evaluation of wave spectrum is a prior art, and can use for example H.N.Cheng by those skilled in the art, Macromolecules17 (1984), the 1950-1955 page or leaf, perhaps L.Abis etc., Makromol.Chemie187 (1986), the method that the 1877-1886 page or leaf is described is carried out.This structure can be passed through " PE then X" and the ratio of " PEP " PE is wherein described XRefer to have 〉=the propylene-ethylene unit of 2 continuous ethylene unit and PEP refers to have isolating ethylene unit between two propylene units propylene-ethylene unit.Preferably the propylene copolymer compositions that obtains from propylene and ethene has 〉=0.75 PEP/PE XRatio, this ratio is preferred 〉=and 0.85 and especially be preferably 0.85 to 2.5 and be 1.0 to 2.0 especially.
Also preferred such propylene copolymer B, its propylene units of introducing subsequently has isotactic structure.
The character of propylene copolymer compositions of the present invention also decides by the viscosity ratio of propylene copolymer B and propene polymer A, i.e. the ratio of the molar mass of the molar mass of disperse phase and matrix.Especially, this influences transparency.
In order to measure viscosity ratio, propylene copolymer compositions can utilize TREF classification (temperature rising elution fractionation) to come classification.Propylene copolymer B is the highest and comprise under 70 ℃ fraction by the merging of dimethylbenzene wash-out in temperature.Propene polymer A obtains from the fraction that is higher than in temperature under 70 ℃ by the merging of dimethylbenzene wash-out.The shear viscosity of polymkeric substance is measured on the component that obtains like this.This mensuration is undertaken by the method based on ISO 6721-10 usually, uses the rotational viscosimeter with plate/plate geometries, diameter=25 millimeter, and scope=0.05-0.5, warm up time=10-12 minute, temperature was 200 to 230 ℃.The ratio of the shear viscosity of the shear viscosity of propylene copolymer B and propene polymer A is at 100s -1Shearing rate under report.
In preferred propylene copolymer compositions, the ratio of the shear viscosity of the shear viscosity of propylene copolymer B and propene polymer A is at 100s -1Shearing rate under be 0.3 to 2.5, preferred 0.5 to 2 and especially preferred 0.7 to 1.75.
Propylene copolymer compositions of the present invention preferably has narrow molar mass distribution Mw/Mn.For purpose of the present invention, molar mass distribution Mw/Mn is the ratio of weight-average molar mass Mw and mumber average molar mass Mn.Molar mass distribution Mw/Mn is preferably 1.5 to 3.5, especially preferred 2 to 2.5 and especially 2 to 2.3.
The molar mass of Mn of propylene copolymer compositions of the present invention is preferably 20,000g/mol to 500,000g/mol, especially preferred 50,000g/mol to 200,000g/mol and very especially preferred 80,000g/mol to 150,000g/mol.
The present invention provides preparation to be present in the method for the propene polymer in the propylene copolymer compositions of the present invention in addition.This preferably carries out in multistage polymerization process, and it comprises at least two successive polymerization steps, and they usually carry out in the reactor cascade.Can use common being used to prepare the reactor of propene polymer.
Polymerization can be in known manner in body, in suspensoid, in gas phase or in supercritical medium, carry out.It can carry out off and on, perhaps preferably carries out continuously.Solution methods, suspension process, stirring gas phase process or gas fluidized bed method are possible.As solvent or suspension medium, can use the inert hydro carbons, for example Trimethylmethane, or monomer itself.Can also in two or more reactors, carry out one or more steps of the inventive method.For method of the present invention, the size of reactor is not critical.This depends on the output that will obtain in single reaction zone.
In the preferable methods, the polymerization in second step of formation propylene copolymer B is carried out from gas phase.Propene polymer A pre-polymerization can be in body (block), promptly in as the liquid propene of suspension medium, carry out, or carry out from gas phase.If all polymerizations take place from gas phase, they preferably carry out in the cascade of the Gas-phase reactor that comprises placed in-line stirring, and wherein the powdered reaction bed utilizes vertical stirrer to keep motion.Reaction bed generally is made up of polymeric polymkeric substance in corresponding reactor.If the initial polymerization of propene polymer A carries out with body, the then preferred cascade of forming by one or more annular-pipe reactors and one or more gas-phase fluidized-bed reactor that uses.This preparation can also be carried out in the multi-region reactor.
In order to prepare the propene polymer that is present in the propylene copolymer compositions of the present invention, the preferred catalyst system that uses based on the metallocene compound of the transition metal of the family 3,4,5 of the periodic table of elements or 6.
The particularly preferred catalyst system that is based on the metallocene compound of general formula (I):
Figure A0381342600121
Wherein,
M is zirconium, hafnium or titanium, preferred zirconium,
X is identical or different, and be independently of each other separately hydrogen or halogen or-R ,-OR ,-OSO 2CF 3,-OCOR ,-SR ,-NR 2Perhaps-PR 2Group, wherein R is straight or branched C 1-C 20-alkyl, C 3-C 20-cycloalkyl, they can be by one or more C 1-C 10-alkyl replaces, C 6-C 20-aryl, C 7-C 20-alkylaryl or C 7-C 20-arylalkyl, and can comprise heteroatoms or the one or more unsaturated link(age) of the 13-17 of family of one or more periodic table of elements, preferred C 1-C 10-alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl or C for example 3-C 20-cycloalkyl is cyclopentyl or cyclohexyl for example, and wherein two radicals X can also interconnect and be preferably formed C 4-C 40-dialkylene ligand, butadienyl ligand especially, perhaps-and OR ' O-group, wherein substituent R ' be divalent group, it is selected from C 1-C 40-alkylidene, C 6-C 40-arylidene, C 7-C 40-alkyl arylene and C 7-C 40-aryl alkylidene,
Wherein X preferably halogen atom or-R or-the OR group, perhaps two radicals X formation-OR ' O-groups, and X are chlorine or methyl especially preferably,
L is the divalence bridge linkage group, and it is selected from C 1-C 20-alkylidene, C 3-C 20-ring alkylidene, C 6-C 20-arylene group, C 7-C 20-alkyl arylene group and C 7-C 20-aryl alkylidene group, the heteroatoms that it can containing element subgroup 13-17 perhaps has the silicylene of maximum 5 Siliciumatoms, for example-SiMe 2-or-SiPh 2-,
Wherein L preferably is selected from-SiMe 2-,-SiPh 2-,-SiPhMe-,-SiMe (SiMe 3)-,-CH 2-,-(CH 2) 2-,-(CH 2) 3-and-C (CH 3) 2-group,
R 1Be straight or branched C 1-C 20-alkyl, C 3-C 20-cycloalkyl, they can be by one or more C 1-C 10-alkyl replaces, C 6-C 20-aryl, C 7-C 20-alkylaryl or C 7-C 20-arylalkyl and can comprise heteroatoms or one or more unsaturated link(age), the wherein R of the 13-17 of family of one or more periodic table of elements 1Preferably be unbranched and unbranched straight or branched C preferably in the α position in the α position 1-C 10-alkyl group, especially straight chain C 1-C 4-alkyl group is methyl, ethyl, n-propyl or normal-butyl for example,
R 2Be general formula-C (R 3) 2R 4Group, wherein
R 3Be identical or different, and be straight or branched C separately independently of each other 1-C 20-alkyl, C 3-C 20-cycloalkyl, they can be by one or more C 1-C 10-alkyl replaces, C 6-C 20-aryl, C 7-C 20-alkylaryl or C 7-C 20-arylalkyl and can comprise heteroatoms or the one or more unsaturated link(age) of the 13-17 of family of one or more periodic table of elements, perhaps two radicals R 3Can be connected to form saturated or unsaturated C 3-C 20-ring,
R wherein 3Straight or branched C preferably 1-C 10-alkyl group and
R 4Be hydrogen or straight or branched C 1-C 20-alkyl, C 3-C 20-cycloalkyl, they can be by one or more C 1-C 10-alkyl replaces, C 6-C 20-aryl, C 7-C 20-alkylaryl or C 7-C 20-arylalkyl and can comprise heteroatoms or the one or more unsaturated link(age) of the 13-17 of family of one or more periodic table of elements,
R wherein 4Hydrogen preferably,
T and T ' are general formula (II), (III), (IV), (V) or divalent group (VI),
Figure A0381342600131
Wherein the atom of representing by symbol * and * * be connected to general formula (I) compound by the atom of identical symbolic representation and
R 5Be identical or different, and be hydrogen or halogen or straight or branched C separately independently of each other 1-C 20-alkyl, C 3-C 20-cycloalkyl, they can be by one or more C 1-C 10-alkyl replaces, C 6-C 20-aryl, C 7-C 20-alkylaryl or C 7-C 20-arylalkyl and can comprise heteroatoms or the one or more unsaturated link(age) of the 13-17 of family of one or more periodic table of elements, wherein
R 5Preferably hydrogen or straight or branched C 1-C 10-alkyl group, especially straight chain C 1-C 4-alkyl group for example methyl, ethyl, n-propyl or normal-butyl and
R 6Be identical or different, and be halogen or straight or branched C separately independently of each other 1-C 20-alkyl, C 3-C 20-cycloalkyl, they can be by one or more C 1-C 10-alkyl replaces, C 6-C 20-aryl, C 7-C 20-alkylaryl or C 7-C 20-arylalkyl and can comprise heteroatoms or the one or more unsaturated link(age) of the 13-17 of family of one or more periodic table of elements, wherein
R 6The aromatic yl group of general formula (VII) preferably,
R 7Be identical or different, and be hydrogen or halogen or straight or branched C separately independently of each other 1-C 20-alkyl, C 3-C 20-cycloalkyl, they can be by one or more C 1-C 10-alkyl replaces, C 6-C 20-aryl, C 7-C 20-alkylaryl or C 7-C 20-arylalkyl and can comprise heteroatoms or the one or more unsaturated link(age) of the 13-17 of family of one or more periodic table of elements, perhaps two radicals R 7Can be connected to form saturated or unsaturated C 3-C 20Ring,
R wherein 7Preferably hydrogen atom and
R 8Be hydrogen or halogen or straight or branched C 1-C 20-alkyl, C 3-C 20-cycloalkyl, they can be by one or more C 1-C 10-alkyl replaces, C 6-C 20-aryl, C 7-C 20-alkylaryl or C 7-C 20-arylalkyl and can comprise heteroatoms or the one or more unsaturated link(age) of the 13-17 of family of one or more periodic table of elements,
R wherein 8General formula-C (R preferably 9) 3Branched alkyl group, wherein
R 9Be identical or different, and be straight or branched C separately independently of each other 1-C 6-alkyl group or radicals R 9Two or three be connected to form one or more ring systems.
At least one of preferred group T and T ' is by the radicals R of general formula (VII) 6Replace; Especially preferred is that two groups are all replaced by such group.Very particularly preferably be, at least one of group T and T ' is the group of general formula (IV), it is by the radicals R of general formula (VII) 6Replace, and another has general formula (II) or (IV) and equally by the radicals R of general formula (VII) 6Replace.
The most preferred catalyst system that is based on the metallocene compound of general formula (VIII),
Figure A0381342600151
Metallocene compound that is particularly useful and their method of preparation are described in for example WO01/48034 and european patent application 01204624.9.
The metallocene compound of general formula (I) preferably uses with racemize (rac) or false racemize (pseudorac) form, wherein false racemic form is a kind of complex compound, wherein when not considering every other substituting group, two group T and T ' are in racemize mutually and arrange.This class metallocene causes mainly having the polypropylene of isotactic structure.
Can also use the mixture of various metallocene compounds or the mixture of various catalyst systems.Yet, only a kind of catalyst system that comprises a kind of metallocene compound of preferred use, this metallocene compound is used for the polymerization of propene polymer A and propylene copolymer B.
The example of useful metallocene compound is
Dimethylsilane two bases (2-ethyl-4-(4 '-tert-butyl-phenyl) indenyl) (2-sec.-propyl-4-(4 '-tert-butyl-phenyl) indenyl) zirconium dichloride,
Dimethylsilane two bases (2-methyl-4-(4 '-tert-butyl-phenyl) indenyl) (2-sec.-propyl-4-(1-naphthyl) indenyl) zirconium dichloride,
Dimethylsilane two bases (2-methyl-4-phenyl-1-indenyl) (2-sec.-propyl-4-(4 '-tert-butyl-phenyl)-1-indenyl) zirconium dichloride,
Dimethylsilane two bases (2-methyl sulfo-pentenyl) (2-sec.-propyl-4-(4 '-tert-butyl-phenyl) indenyl) zirconium dichloride,
Dimethylsilane two bases (2-sec.-propyl-4-(4 '-tert-butyl-phenyl) indenyl) (2-methyl-4,5-benzo indenyl) zirconium dichloride,
Dimethylsilane two bases (2-methyl-4-(4 '-tert-butyl-phenyl) indenyl) (2-sec.-propyl-4-(4 '-tert-butyl-phenyl) indenyl) zirconium dichloride,
Dimethylsilane two bases (2-methyl-4-(4 '-tert-butyl-phenyl) indenyl) (2-sec.-propyl-4-phenyl indenyl) zirconium dichloride,
Dimethylsilane two bases (2-ethyl-4-(4 '-tert-butyl-phenyl) indenyl) (2-sec.-propyl-4-phenyl) indenyl) zirconium dichloride and
Dimethylsilane two bases (2-sec.-propyl-4-(4 '-tert-butyl-phenyl) indenyl) (2-methyl-4-(1-naphthyl) indenyl) zirconium dichloride and composition thereof.
Preferably the catalyst system based on metallocene compound usually also comprises the compound that can form as the metallocene ion (metallocenium) of promotor.This compounds that is fit to comprises strong, uncharged Lewis acid, has the Lewis-cationic ionic compound of acid and comprises Br nsted acid as cationic ionic compound.Example is three (pentafluorophenyl group) borine, four (pentafluorophenyl group) borate or N, the salt of accelerine.The same conduct that is fit to can form the metallocene ion and be open chain or cyclic aluminium alkoxide compound as the compound of promotor therefore.These are usually by trialkylaluminium and water prepared in reaction, and usually are the form of mixtures of the straight chain and the ring-type chain molecule of all lengths.Preferably the catalyst system based on metallocene compound uses with the form of load usually.The carrier that is fit to is for example organic or inorganic inert solids of porous, for example polymer powder of fine dispersion or inorganic oxide, for example silica dioxide gel.Metallocene catalyst system can also containing element subgroup 1,2 and the organometallic compound of 13 metal, for example n-Butyl Lithium or aluminum alkyls.
In preparation is present in propene polymer in the propylene copolymer compositions of the present invention, preferably at first in first step, by from being the propylene of 90% weight based on the mixture total weight amount to 100% weight, there is other alkene or do not existing under the condition of other alkene, usually under the pressure of 40 ℃ to 120 ℃ and 0.5 to 200 crust, by polymerization formation propene polymer A.Subsequently in second step, at the mixture of other alkene of propylene that utilizes polymerization 2 to 95% weight on the polymkeric substance of this prepared in reaction and 5% to 98% weight, this step is carried out under 40 ℃ to 120 ℃ and 0.5 pressure that cling to 200 crust usually.The polymerization of propene polymer A preferably 60 to 80 ℃, especially preferred 65 to 75 ℃ and 5 to 100 the crust pressure, especially preferred 10 cling to 50 the crust pressure under carry out.The polymerization of propylene copolymer B preferably 60 to 80 ℃, especially preferred 65 to 75 ℃ and 5 to 100 the crust pressure, especially preferred 10 cling to 50 the crust pressure under carry out.
In polymerization, can use common additive, for example molar mass regulator for example nitrogen or argon gas of hydrogen or rare gas element for example.
To the monomeric amount that in single step, adds and processing condition for example pressure, temperature or molar mass regulator for example the adding of hydrogen select, make the polymkeric substance that forms have the character of hope.Scope of the present invention comprises that industry is open, it is propylene copolymer compositions, it has good low-temperature impact toughness and simultaneously good transparency and good stress whitening proterties, can be for example the co-monomer content of definition by setting propylene copolymer B and the viscosity of propene polymer A and propylene copolymer B recently obtain.
The composition of propylene copolymer B has tangible influence to the transparency of propylene copolymer compositions of the present invention.The reduction of the co-monomer content of propylene copolymer B causes improved transparency, yet the toughner of low-temperature impact simultaneously reduces.The co-monomer content raising of propylene copolymer B causes low-temperature impact toughness to improve, but transparency reduces.Simultaneously, can also improve impelling strength by the ratio that improves propylene copolymer B.Therefore, product of the present invention shows the comprehensive of these favourable character, has promptly obtained to have simultaneously the opaque products of good low-temperature impact toughness.Use under the situation of ethene as comonomer preferred, especially preferably the ethylene content of propylene copolymer B is set at 10 to 20% weight, especially 12 to 18% weight and preferably approximately 16% weight especially.The transparency of propylene copolymer compositions of the present invention is irrelevant with the ratio of the propylene copolymer B that wherein exists in fact.
Regulate the dispersion of viscosity ratio impact propylene copolymer B in polymeric matrix of propene polymer A and propylene copolymer B, and therefore influential to the transparency and the mechanical property of propylene copolymer compositions.
Propylene copolymer compositions of the present invention shows good low-temperature impact toughness, and it also has good transparency and good stress whitening proterties concurrently, and higher melt, high stiffness and good resistance to heat distorsion.This propylene copolymer compositions also has low extracted content, uniform comonomer distribution and good organoleptic properties.Because fragility/ductility transmition temperature is lower than-15 ℃, propylene copolymer compositions of the present invention can also be used for the material property of heterophasic copolymer under temperature under the freezing point is had the temperature range of high request.This provides new widely possibility for propylene copolymer compositions of the present invention uses in the clear applications at low temperatures.
Heterophasic copolymer of the present invention is suitable for producd fibers, film or moulded parts, in particular for producing injection mould plastic, film, sheet material or big ducted body, for example utilizes injection-molded or expressing technique production the said products.Possible application is following field: wrapping material, household supplies, the container that is used for storage and transport, office's goods, electric installation, toy, labware, trolley part and garden supplies are particularly useful for lower temperature application in each case.
The present invention illustrates by following preferred embodiment, and these embodiment do not limit the scope of the invention:
Embodiment
Embodiment and comparative example use the process of the embodiment 98 to 102 that is similar to WO 01/48034 to carry out, and Comparative Examples A, B and C are corresponding to the embodiment 98,99 and 100 of WO 01/48034.
The preparation of metallocene catalyst
The Sylopol948 of 3kg is placed process filter, and its filter plate downwards and be suspended in 15 liters of toluene.So that internal temperature is no more than 35 ℃ speed stir in, be metered into the MAO solution (from Albemarle) of 7 liter of 30% weight strength.After under low agitator speed, stirring other 1 hour, suspensoid is filtered, at first do not use impressed pressure, under the nitrogen pressure of 3 crust, carry out then.Similar with the processing of solid support material, the MAO solution of 2.0 liter of 30% weight strength is placed reaction vessel, add 92.3 gram racemize-dimetylsilyl (2-methyl-4-(to tert-butyl-phenyl) indenyl) (2-sec.-propyl-4-(to tert-butyl-phenyl) indenyl) zirconium dichlorides, with solution stirring 1 hour and placed other 30 minutes.Subsequently this solution is used for pretreated solid support material, closes outlet.After adding is finished, open outlet, make filtrate outflow.Close outlet subsequently, filter cake was stirred 15 minutes and placed 1 hour.Then outlet is opened, utilize the nitrogen pressure of 3 crust that liquid is extruded from filter cake.15 liters of Permethyl 99A.s are joined in the remaining solid, mixture was stirred 15 minutes and filtered.The repeated washing step, and utilize the nitrogen pressure of 3 crust that filter cake is pressed dry subsequently.For being used for polymerization, the total amount of catalyzer is resuspended in 15 liters the Permethyl 99A..
Polymerization
This technology is placed in-line and have 200 liters of available spaces separately and be equipped with in the agitated autoclave of volution agitator independently and carry out at two.Two reactors comprise the fixed bed of the stirring of fine dispersion propene polymer.
Propylene is fed first polymerization reactor and utilizing metallocene catalyst to carry out polymerization under the average retention time as shown in table 1, under pressure and temperature as shown in table 1 with gaseous form.The amount of metallocene catalyst of metering should make the amount of transferring to the polymkeric substance of second polymerization reactor from first polymerization reactor, and is consistent with the amount that is shown in Table 1 fifty-fifty.The Frisch propylene that metallocene catalyst is regulated pressure with being used to of being added measures.The triethyl aluminum of the form of 1 mole solution also is metered in the reactor in heptane.
The propylene copolymer that obtains in first Gas-phase reactor is transferred in second Gas-phase reactor with active catalyst component still.There, propylene-ethylene copolymers B is aggregated on it, and total pressure, temperature and average retention time are as shown in table 1.Ethylene concentration in reactant gases is monitored by vapor-phase chromatography.The propene polymer A[A (l) that in first reactor, forms] with the propylene copolymer B[B (ll) that in second reactor, forms] weight ratio be shown in table 1.Virahol (with the form of 0.5 molar solution in heptane) also is metered in second reactor.The polymkeric substance that forms in first reactor utilizes Virahol to control with the weight ratio of the polymkeric substance that forms in second reactor, and this Virahol is metered in second reactor with the form of 0.5 molar solution in heptane, and is as shown in table 1.In order to regulate molar mass, as required with in hydrogen metering to the second reactor.The ratio of the propylene-ethylene copolymers B that forms in second reactor is calculated according to following relation by the difference of the amount of amount that shifts and discharging: the output of (output of the output of second reactor-first reactor)/second reactor.
Table 1: polymerizing condition
Embodiment 1 Embodiment 2 Comparative Examples A Comparative example B Comparative example C
Reactor I
Pressure [crust] ????28 ????28 ????28 ????29 ???29
Temperature [℃] ????73.5 ????73 ????75 ????75 ???75
Triethyl aluminum, 1M[ml/h in heptane] ????90 ????90 ????60 ????60 ???60
The residence time [h] ????1.5 ????1.5 ????2.25 ????2.25 ???2.25
(230 ℃/2.16kg) [g/10min]/ISO 1133 of powder MFR ????10.7 ????20 ????11.0 ????9.8 ???9.2
Powder work output [kg/h] ????30 ????20 ????20 ????20 ???20
Reactor II
Pressure [crust] ????15 ????15 ????15 ????15 ???15
Temperature [℃] ????65 ????70 ????65 ????65 ???65
Ethene [% volume] ????36 ????41.5 ????30 ????41 ???49
Hydrogen [standard liter/h *] ????10.6 ????0 ????0 ????0 ???0
The residence time [h] ????1.0 ????1.0 ????1.7 ????1.7 ???1.7
Powder work output [kg/h] ????43.7 ????42.6 ????24.1 ????24.2 ???24.3
(230 ℃/2.16kg) [g/10min]/ISO 1133 of powder MFR ????13 ????13 ????10.7 ????8.7 ???5.5
The content of propene polymer A [weight %] ????69 ????70 ????83 ????83 ???82
The content of propylene-ethylene copolymers B [weight %] ????31 ????30 ????17 ????17 ???18
The weight ratio of A (I): B (II) ????2.2 ????2.4 ????4.9 ???4.8 ???4.7
*) standard liter/h: the standard liter per hour
The polymer powder for preparing in the polymerization is mixed with the standard additive mixture in granulation step.Werner ﹠amp is used in granulation; The twin screw extruder ZSK30 of Pfleiderer carries out under 250 ℃ melt temperature.The propylene copolymer compositions of preparation comprises the Irganox1010 (from Ciba Specialty Chemicals) of 0.05% weight, the Irgafos168 (from Ciba Specialty Chemicals) of 0.05% weight, the calcium stearate of 0.1% weight and the Millad3988 (two-3 of 0.22% weight, 4-dimethyl benzylidene Sorbitol Powder is from Milliken Chemical).
The character of propylene copolymer compositions is shown in table 2 and 3.Measure on the propylene copolymer compositions of these data after adding additive and granulation or on specimen, measure by its production.
Table 2: the analytical results of propylene copolymer compositions
Embodiment 1 Embodiment 2 Comparative Examples A Comparative example B Comparative example C
C 2Content ( 13C-NMR) [weight %] ????5.7 ???6.2 ????2.7 ????5.1 ???10.2
The C of propylene-ethylene copolymers B 2Content ( 13C-NMR) [weight %] ????16.1 ???15.7 ????11.6 ????22.1 ???42.3
Limiting viscosity (ISO 1628) [cm 3/ g] propene polymer A propylene-ethylene copolymers B ????160 ????117 ???148 ???150 ????175 ????152 ????164 ????157 ???185 ???191
PEP( 13C-NMR) [weight %] ????3.97 ???3.94 ????1.5 ????1.7 ???1.7
PE X( 13C-NMR) [weight %] ????4.31 ???4.00 ????1.0 ????2.4 ???4.4
PEP/PE X ????0.92 ???0.99 ????1.5 ????0.71 ???0.39
Second-order transition temperature [℃] (DMTA, ISO 6721-7) ????-2 */ ????-35 ** ???-2 */ ???-33 ** ????-6 *** ????2 */ ???-42 ** ???2 */ ???-56 **
Molar mass of Mn [g/mol] ????82000 ???81000 ????101000 ????95000 ???106000
Molar mass distribution [Mw/Mn] ????2.1 ???2.2 ????2.1 ????2.1 ???2.0
The shear viscosity η of propylene-ethylene copolymers B 100 **** ????162 ???311 ????293 ????382 ???1167
The shear viscosity η of propene polymer A 100 **** ????353 ???182 ????313 ????377 ???404
Ratio (ω=the 100s of the shear viscosity of propylene-ethylene copolymers B/ propene polymer A -1) **** ????0.5 ???1.7 ????0.9 ????1.0 ???2.9
*) second-order transition temperature of propene polymer A
*) second-order transition temperature of propylene-ethylene copolymers B
* *) only measured a value.This is worth corresponding to mixing temperature, and points out that in the comparative example, propene polymer A and propylene-ethylene copolymers B are mixable.
* * *) be at 100s in each case -1Shearing rate under and the shearing rate under 230 ℃ mensuration temperature; Except the embodiment 1, wherein measuring temperature is 220 ℃.
Table 3: the test that relevant propylene copolymer compositions is used
Embodiment 1 Embodiment 2 Comparative Examples A Comparative example B Comparative example C
?MFR(230℃/2.16kg)[g/10min] ?/ISO?1133 ????16.2 ????16.5 ???12.3 ????8.7 ????6.9
The DSC fusing point [℃]/ISO 3146 ????156.0 ????155.9 ???156 ????157.0 ????157.0
Dimension card A softening temperature [℃]/ISO 306VST/A50 ????128 ????127 ???141 ????139 ????140
B[℃ of resistance to heat distorsion HDT]/ISO 75-2 method B ????66 ????64 ???81 ????76 ????78
Stretching E modulus [Mpa]/ISO 527 ????602 ????609 ???1156 ????1006 ????1093
Fragility/ductility transmition temperature [℃] ????-28 ????-23 ???9 ????-15 ????＜-30
Xia Shi impelling strength (+23 ℃) [kJ/m 2] ?/ISO?179-2/1eU ????NF ????NF ???NF ????NF ????NF
Xia Shi impelling strength (0 ℃) [kJ/m 2] ?/ISO?179-2/1eU ????194 ????NF ???163 ????NF ????NF
Xia Shi impelling strength (20 ℃) [kJ/m 2] ?/ISO?179-2/1eU ????265 ????NF ???28 ????180 ????130
Sharpy gap impelling strength (+23 ℃) [kJ/m 2]/ISO?179-2/1eA ????41.3 ????49.4 ???7.6 ????43.7 ????48.8
Sharpy gap impelling strength (0 ℃) [kJ/m 2]/ISO?179-2/1eA ????28.9 ????12.6 ???2.0 ????6.9 ????19.4
Sharpy gap impelling strength (20 ℃) [kJ/m 2]/ISO?179-2/1eA ????2.6 ?????2.1 ???1.4 ????1.5 ????3.3
(1 millimeter of mist degree *)[％]/ASTM ?D1003 ????15 ?????25 ???12 ????35 ????68
(50 microns of mist degrees **)[％]/ASTM ?D1003 ????15 ?????17 ???10 ????20 ????17
Stress whitening (23 ℃) [millimeter]/vault method ????0 ?????0 ????0 ????9.4 ????12.0
NF: do not rupture
*) injection-molded plate, its thickness is 1 millimeter.
*) film, its thickness is 50 microns (not observing clearly mist degree dependency)
Compare with Comparative Examples A, propylene copolymer compositions of the present invention has improved toughness, especially at low temperatures.Compare with C with comparative example B, obtained transparency significantly preferably, and do not have significant toughness to worsen.
Analyze
Be used for carrying out with the production of the specimen of using relevant test and the standard that test itself is pointed out according to table 3.
In order to measure the analytical data of product fraction, utilize TREF, in dimethylbenzene with the preparation polymkeric substance or polymer composition classification, describe as L.Wild, " TemperatureRising Elution Fractionation ", Advanced Polym.Sci.98,1-47,1990.Fraction is at 40,70,80,90,95,100,110 and 125 ℃ of following wash-outs and be appointed as the propene polymer A for preparing or the propylene copolymer B for preparing in reactor II in reactor I.As propylene-ethylene copolymers B, use the highest and comprise the fraction of the merging of 70 ℃ of following TREF wash-outs in temperature.As propene polymer A, use the fraction of the merging that is higher than 70 ℃ of following TREF wash-outs.
Fragility/ductility transmition utilizes the punching press of describing among the ISO 6603-2/40/20/C/4.4 to measure.The speed of drift is elected 4.4m/s as, and the support ring diameter is that 40 millimeters diameters with the bump ring are 20 millimeters.Specimen is sandwiched in wherein.The geometrical dimension of specimen is 6 centimetres of 6 cm x, and thickness is 2 millimeters.In order to measure the temperature dependency curve, test is carried out at the step with 2 ℃ from 26 ℃ to-35 ℃ temperature range, wherein uses the specimen that is preheated/is pre-chilled to relevant temperature.
In this embodiment, fragility/ductility transmition determined by total deformation (unit millimeter), this total deformation be defined as when power by maximum value and be reduced to maximum value power 3% the time drift displacement of moving.For purpose of the present invention, fragility/ductility transmition temperature is defined as such temperature, and total deformation is lower than the average total deformation at least 25% of 5 measurement point the preceding under this temperature.
The mensuration of haze value is carried out according to standard A STM D1003.This value is to the sample determination of the Millad3988 that comprises 2200ppm.Specimen is to have 6 * 6 centimetres the edge length and the injection-molded plate of 1 millimeter thickness.Specimen is under 250 ℃ the melt temperature and injection moulding under 30 ℃ the tool surfaces temperature.In order to measure the haze value of film, producing thickness by compacting is 50 microns film.Be under the room temperature through being used for after 7 days storage time of post crystallization (after-crystallization), specimen is sandwiched the gripping unit that enters the front, hole that is positioned at Hazegard System XL 211 (from Pacific Scientific), measure subsequently.Test is carried out under 23 ℃, and each specimen in interim test once.In order to obtain mean value, test 5 specimen in each case.
The stress whitening proterties is utilized the evaluation of vault method.In the vault method, stress whitening utilizes the dart measuring apparatus, and as DIN 53443 parts 1 defined, functional quality is the dart of 250 grams, and it is 25 millimeters with the vault radius that punch diameter is 5 millimeters.The journey that falls is 50 centimetres.As specimen, use injection-molded disk, it is 2 millimeters with thickness that its diameter is 60 millimeters.Specimen is under 250 ℃ the melt temperature and injection moulding under 30 ℃ the tool surfaces temperature.Test is carried out under 23 ℃, and each specimen is carried out shock test only once.At first specimen is placed on the support ring, and does not clamp, discharge dart subsequently.In order to obtain mean value, test at least five specimen.The diameter in visible stress whitening zone reports with millimeter, and by flow direction and with the opposite circular side, side that bump takes place on measure with the vertical direction of flow direction, and obtain the mean value of two values.
C 2The structure utilization of content and propylene-ethylene copolymers 13The C-NMR spectroscopy determining.
The E modulus is measured according to ISO 527-2:1993.Injection moulding has 1 type specimen of 150 millimeters total lengths and 80 millimeters parallel sectionss under the tool surfaces temperature of 250 ℃ melt temperatures and 30 ℃.In order to carry out post crystallization, specimen was preserved 7 days under the standard conditions of 23 ℃/50% atmospheric moisture.To be used for test from the Z022 type testing apparatus of Zwick-Roell.In the mensuration of E modulus, the determining displacement system has 1 micron resolving power.Test speed is 1 mm/min in the mensuration of E modulus, perhaps 50 mm/min.Yield-point is the scope of 0.05%-0.25% in the mensuration of E modulus.
Measurement of melting point utilizes DSC (dsc) to carry out.Mensuration is carried out according to iso standard 3146, use first heating steps to be heated to the highest 200 ℃ with the heating rate of 20 ℃ of per minutes, reduce to 25 ℃ with the rate of cooling of 20 ℃ of per minutes and carry out dynamic crystallization, and second heating steps with the heating rate reheat of 20 ℃ of per minutes to the highest 200 ℃.Fusing point is that enthalpy at second heating steps period detecting is to the peaked temperature of the curve display of temperature.
The mensuration of molar mass of Mn and molar mass distribution Mw/Mn is undertaken by gel permeation chromatography (GPC), and temperature is 145 ℃, 1,2, carries out in the 4-trichlorobenzene, uses the 150C type GPC equipment of Waters.Be used to mbH, the described data of Win-GPC software evaluation of Ober-Hilbersheim from HS-Entwicklungsgesellschaft f ü rwissenschaftliche Hard-und Software.It is 100 to 10 that pillar utilizes molar mass 7The polypropylene standard model calibration of g/mol.
Limiting viscosity, promptly being determined in the naphthane of ultimate value of the viscosity number when polymer concentration is pushed out to zero carried out according to ISO 1628 under 135 ℃.
Shear viscosity is by measuring based on the method for ISO 6721-10 (the RDS equipment with plate/plate geometries, diameter=25 millimeter, scope=0.05-0.5, warm up time=10-12 minute, T=200-230 ℃).The ratio of the shear viscosity of propylene copolymer B and propylene copolymer A is at 100s -1Shearing rate under measure.Measuring temperature is 220-230 ℃.
In order to utilize DMTA to measure second-order transition temperature according to ISO 6721-7, extrude from the sheet material patrix and to be of a size of 10mm * 60mm and thickness is the specimen of 1mm, described sheet material is suppressed from melt, 210 ℃, under 30 crust 7 minutes, the rate of cooling=15K/min of compacting after finishing.Be clipped in specimen in the described equipment and under-100 ℃, begin and test.Heating rate is that 2.5K/min and test frequency are 1 hertz.

Claims (15)

1. propylene copolymer compositions, it comprises:
A) propene polymer, its comprise 0 to 10% vary in weight in the alkene of propylene and
B) at least a propylene copolymer, it comprises the alkene that is different from propylene of 5 to 40% weight,
Wherein, propene polymer A exists as isolating mutually with propylene copolymer B, and
The haze value of propylene copolymer compositions≤30%, based on the path length of 1 millimeter propylene copolymer compositions and the fragility of propylene copolymer compositions/ductility transmition temperature be≤-15 ℃.
2. the propylene copolymer compositions of claim 1, wherein propene polymer A is an alfon.
3. claim 1 or 2 propylene copolymer compositions, wherein propene polymer A has isotactic structure.
4. any one propylene copolymer compositions of claim 1 to 3, the alkene that wherein is different from propylene is ethene individually.
5. any one propylene copolymer compositions of claim 1 to 4 is 0 to 8 millimeter by the vault method in the value of 23 ℃ of stress whitenings of measuring down wherein.
6. any one propylene copolymer compositions of claim 1 to 5, wherein the weight ratio of propene polymer A and propylene copolymer B is 90: 10 to 60: 40.
7. any one propylene copolymer compositions of claim 1 to 6, wherein multipolymer B is dispersed among the matrix A with the fine dispersion form.
8. any one propylene copolymer compositions of claim 1 to 7, the content that wherein is different from the alkene of propylene in multipolymer B is 7 to 25% weight.
9. any one propylene copolymer compositions of claim 1 to 8, it comprises based on the propylene copolymer compositions gross weight is the nucleator of 0.1 to 1 weight %.
10. any one propylene copolymer compositions of claim 1 to 9 wherein utilizes the second-order transition temperature of the propylene copolymer B that DMTA (dynamic mechanics heat analysis) measures to be-20 ℃ to-40 ℃.
11. any one propylene copolymer compositions of claim 1 to 10, wherein under the shearing rate of 100s-1, the ratio of the shear viscosity of propylene copolymer B and propene polymer A is 0.3 to 2.5.
12. any one propylene copolymer compositions of claim 1 to 11, wherein molar mass distribution Mw/Mn is 1.5 to 3.5.
13. be used to prepare any one the method for propylene copolymer compositions of claim 1 to 12, wherein carry out multistage polymerization and use catalyst system based on metallocene compound.
14. any one propylene copolymer compositions of claim 1 to 12 is used for the purposes of producd fibers, film or moulded parts.
15. a fiber, film or moulded parts, it comprises, preferably as basal component, and any one propylene copolymer compositions of claim 1 to 12.
CN03813426.8A 2002-06-12 2003-06-10 Propylene copolymer compositions having a good low-temperature impact toughness and a high transparency Expired - Lifetime CN1290917C (en)

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CN107903499A (en) * 2017-12-04 2018-04-13 天津科技大学 A kind of transparent toughening modifying polypropylene plastics and its preparation

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